US7511084B2 - Acyl- and bisacylphosphine derivatives - Google Patents

Acyl- and bisacylphosphine derivatives Download PDF

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US7511084B2
US7511084B2 US10/502,658 US50265804A US7511084B2 US 7511084 B2 US7511084 B2 US 7511084B2 US 50265804 A US50265804 A US 50265804A US 7511084 B2 US7511084 B2 US 7511084B2
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Ralf Noe
Andreas Henne
Matthias Maase
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IGM Group BV
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3294—Compounds containing the structure R2P(=X)-X-acyl, R2P(=X)-X-heteroatom, R2P(=X)-X-CN (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/32—Esters thereof
    • C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/3247—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se)
    • C07F9/3252—Esters of acids containing the structure -C(=X)-P(=X)(R)(XH) or NC-P(=X)(R)(XH), (X = O, S, Se) containing the structure -C(=X)-P(=X)(R)(XR), (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/34—Halides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
    • C07F9/36—Amides thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4062—Esters of acids containing the structure -C(=X)-P(=X)(XR)2 or NC-P(=X)(XR)2, (X = O, S, Se)
    • C07F9/4065—Esters of acids containing the structure -C(=X)-P(=X)(XR)2, (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/409—Compounds containing the structure P(=X)-X-acyl, P(=X) -X-heteroatom, P(=X)-X-CN (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/409—Compounds containing the structure P(=X)-X-acyl, P(=X) -X-heteroatom, P(=X)-X-CN (X = O, S, Se)
    • C07F9/4093—Compounds containing the structure P(=X)-X-C(=X)- (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/409—Compounds containing the structure P(=X)-X-acyl, P(=X) -X-heteroatom, P(=X)-X-CN (X = O, S, Se)
    • C07F9/4096—Compounds containing the structure P(=X)-X-N (X = O, S, Se)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/42—Halides thereof
    • C07F9/425—Acid or estermonohalides thereof, e.g. RP(=X)(YR)(Hal) (X, Y = O, S; R = H, or hydrocarbon group)
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur

Definitions

  • the present invention relates to reactive acyl- and bisacylphosphine derivatives, to a process for their preparation, and to their use.
  • JP 10-62927, JP 9-152689, EP-A 724 194 and JP 3-10241 disclose compounds having a phosphine oxide structure which carry a hydroxylamino or alkoxylamino group or a hydrazido group on the central phosphorus atom and which are used in photographic materials.
  • U.S. Pat. No. 5,683,615 discloses magnetorheological liquids which comprise dialkyl dithiophosphates.
  • acylphosphine oxides for example those which carry an unsubstituted or substituted amino group, a hydroxyl group or an —O-M + group, where M + is an equivalent of a cation, on the central phosphorus atom (EP-A 62 839), a C 1 -C 12 -alkoxy group (DE-A 196 50 562), an aryloxy group (EP-A 600 373) or a silyloxy group (EP-A 487 453), and which can likewise be used as photoinitiators.
  • EP-B 7 508 discloses the synthesis of acylphosphine oxides in an Arbusov rearrangement by reaction of alkoxyphosphines and acid chlorides:
  • U.S. Pat. No. 5,472,992 discloses the synthesis of bisacylphosphines in which a phosphine is diacylated in the presence of a base and subsequently oxidized.
  • WO 00/32612 furthermore discloses the synthesis of acyl- and bisacylphosphines in which an organic phosphoryl halide is brought into contact with an alkali metal or magnesium/lithium, and the resultant metallated phosphines are then reacted with an acid chloride:
  • C 1 -C 18 -alkyl which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, 2,4,4-trimethylpentyl, decyl, dodecyl, tetradecyl, heptadecyl, octadecyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1,3,3-tetramethylbutyl, benzyl, 1-phenylethyl, 2-phenylethyl, ⁇ , ⁇ -dimethylbenzyl, benzhydryl, p-
  • C 1 -C 18 -alkoxy which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals is, for example, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, 6-hydroxy-1,4-dioxohexyl, 9-hydroxy-1,4,7-trioxononyl, 12-hydroxy-1,4,7,10-tetraoxododecyl, 6-methoxy-1,4-dioxohexyl, 9-methoxy-1,4,7-trioxononyl, 12-methoxy-1,4,7,10-tetraoxododecyl, 6-ethoxy-1,4-dioxohexyl, 9-ethoxy-1,4,7-trioxononyl, 12-meth
  • C 2 -C 18 -alkyl which is uninterrupted or interrupted by one or more oxygen and/or sulfur atoms and/or one or more substituted or unsubstituted imino groups is, for example, 5-hydroxy-3-oxapentyl, 8-hydroxy-3,6-dioxaoctyl, 11-hydroxy-3,6,9-trioxaundecyl, 7-hydroxy-4-oxaheptyl, 11-hydroxy-4,8-dioxaundecyl, 15-hydroxy-4,8,12-trioxapentadecyl, 9-hydroxy-5-oxanonyl, 14-hydroxy-5,10-oxatetradecyl, 5-methoxy-3-oxapentyl, 8-methoxy-3,6-dioxaoctyl, 11-methoxy-3,6,9-trioxaundecyl, 7-methoxy-4-oxaheptyl, 11-methoxy-4,
  • the number of oxygen atoms and/or sulfur atoms and/or imino groups is unrestricted. In general, it is not more than 5 in the radical, preferably not more than 4 and very particularly preferably not more than 3.
  • At least one carbon atom preferably at least two carbon atoms, are located between two heteroatoms.
  • Substituted and unsubstituted imino groups can be, for example, imino, methylimino, iso-propylimino, n-butylimino or tert-butylimino.
  • C 2 -C 18 -alkenyl which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals is, for example, vinyl, 1-propenyl, allyl, methallyl, 1,1-dimethylallyl, 2-butenyl, 2-hexenyl, octenyl, undecenyl, dodecenyl, octadecenyl, 2-phenylvinyl, 2-methoxyvinyl, 2-ethoxyvinyl, 2-methoxyallyl, 3-methoxyallyl, 2-ethoxyallyl, 3-ethoxyallyl or 1- or 2-chlorovinyl,
  • C 6 -C 12 -aryl which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals is, for example, phenyl, tolyl, xylyl, ⁇ -naphthyl, ⁇ -naphthyl, 4-biphenylyl, chlorophenyl, dichlorophenyl, trichlorophenyl, difluorophenyl, methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, diethylphenyl, iso-propylphenyl, tert-butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, methylnaphthyl, isopropylnaphthyl, chlorona
  • C 5 -C 12 -cycloalkyl which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals is, for example, cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, methylcyclopentyl, dimethylcyclopentyl, methylcyclohexyl, dimethylcyclohexyl, diethylcyclohexyl, butylcyclohexyl, methoxycyclohexyl, dimethoxycyclohexyl, diethoxycyclohexyl, butylthiocyclohexyl, chlorocyclohexyl, dichlorocyclohexyl, dichlorocyclopentyl and a saturated or unsaturated bicyclic system, for example norbornyl or norbornenyl,
  • a five- to six-membered, oxygen, nitrogen and/or sulfur atom-containing heterocyclic radical is, for example, furyl, thiophenyl, pyrryl, pyridyl, indolyl, benzoxazolyl, dioxolyl, dioxyl, benzimidazolyl, benzothiazolyl, dimethylpyridyl, methylquinolyl, dimethylpyrryl, methoxyfuryl, dimethoxypyridyl, difluoropyridyl, methylthiophenyl, isopropylthiophenyl or tert-butylthiophenyl,
  • C 1 to C 4 -alkyl is, for example, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl or tert-butyl, and
  • C 6 -C 12 -aryl or arylsulfonyl each which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, is, for example, phenyl, 2,6-dinitrophenyl, 2,4-dinitrophenyl, 2-nitrophenyl, 4-nitrophenyl, formyl, acetyl, propionyl, carbamoyl, phenylsulfonyl or 4-methylphenylsulfonyl.
  • the number of substituents in the stated radicals is unrestricted. In general, it is up to 3 substituents, preferably up to 2 substituents and particularly preferably up to one substituent, in radicals having from one to three carbon atoms. In radicals having from four to six carbon atoms, it is generally up to 4 substituents, preferably up to 3 substituents and particularly preferably up to one substituent. In radicals having more than seven carbon atoms, it is generally up to 6 substituents, preferably up to 4 substituents and particularly preferably up to two substituents.
  • R 1 is preferably phenyl, tolyl, xylyl, ⁇ -naphthyl, ⁇ -naphthyl, 2-, 3- or 4-chlorophenyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2-, 3- or 4-methylphenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- or 4-ethylphenyl, 2,6- or 2,4-diethylphenyl, 2-, 3- or 4-iso-propylphenyl, 2-, 3- or 4-tert-butylphenyl, 2-, 3- or 4-methoxyphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl
  • R 1 is particularly preferably phenyl, tolyl, ⁇ -naphthyl, ⁇ -naphthyl, 2,6- or 2,4-dichlorophenyl, 2,4,6-trichlorophenyl, 2,6- or 2,4-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6- or 2,4-diethylphenyl, 2-iso-propylphenyl, 2-tert-butylphenyl, 2,6- or 2,4-dimethoxyphenyl, 2,6- or 2,4-diethoxyphenyl, methylnaphthyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 2,6-dinitrophenyl, 2,5-dimethylcyclopentyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl
  • R 1 is very particularly preferably phenyl, ⁇ -naphthyl, 2,6-dichlorophenyl, 2,4,6-trichlorophenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-diethylphenyl, 2,6-dimethoxyphenyl, 2,6-diethoxyphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2,6-dimethoxyphenyl, 2,6-dichlorophenyl, 2,6-dinitrophenyl, 2,6-dimethylcyclohexyl, 2,6-diethylcyclohexyl, 2,6-dimethoxycyclohexyl, 2,6-diethoxycyclohexyl or 2,6-dichlorocyclohexyl.
  • R 1 is in particular phenyl, 2,6-dichlorophenyl, 2,4,6-trichlorophenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl or 2,6-dimethoxyphenyl.
  • R 2 is preferably 2,4,4-trimethylpentyl, benzyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, 6-hydroxy-1,4-dioxohexyl, 9-hydroxy-1,4,7-trioxononyl, 12-hydroxy-1,4,7,10-tetraoxododecyl, 6-methoxy-1,4-dioxohexyl, 9-methoxy-1,4,7-trioxononyl, 12-methoxy-1,4,7,10-tetraoxododecyl, 6-ethoxy-1,4-dioxohexyl, 9-methoxy-1,4,7-trioxononyl, 12-methoxy-1,4,
  • R 2 is particularly preferably benzyl, p-chlorobenzyl, 2,4-dichlorobenzyl, p-methoxybenzyl, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, 6-hydroxy-1,4-dioxohexyl, 9-hydroxy-1,4,7-trioxononyl, 12-hydroxy-1,4,7,10-tetraoxododecyl, 6-methoxy-1,4-dioxohexyl, 9-methoxy-1,4,7-trioxononyl, 12-methoxy-1,4,7,10-tetraoxododecyl, 6-ethoxy-1,4-dioxohexyl, 9-ethoxy-1,4,7-trioxononyl, 12-methoxy-1,4,7,10-tetraoxo
  • R 2 is very particularly preferably methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, iso-butoxy, tert-butoxy, 6-hydroxy-1,4-dioxohexyl, 9-hydroxy-1,4,7-trioxononyl, 12-hydroxy-1,4,7,10-tetraoxododecyl, 8-hydroxy-1,5-dioxooctyl, 12-hydroxy-1,5,9-trioxooctyl, 16-hydroxy-1,5,9,13-tetraoxohexadecyl, 10-hydroxy-1,6-dioxodecyl, 15-hydroxy-1,6,11-trioxopentadecyl, phenyl, xylyl, ⁇ -naphthyl, ⁇ -naphthyl, 4-biphenylyl, 2-, 3- or 4-chlorophenyl, 2,
  • Y is preferably O, S or NR 3 .
  • Y is particularly preferably O or S and very particularly preferably O.
  • Z is preferably O, S, NR 3 or a free pair of electrons, particularly preferably O, S or a free pair of electrons, very particularly preferably O or S and in particular O.
  • R 3 is preferably hydrogen, methyl, tert-butyl, phenyl or SO 3 H, particularly preferably hydrogen, tert-butyl, phenyl or SO 3 H and very particularly preferably hydrogen, tert-butyl or phenyl.
  • R 4 is preferably hydrogen, methyl, phenyl, 2,4-dinitrophenyl, carbamoyl, phenylsulfonyl or 4-methylphenylsulfonyl, particularly preferably hydrogen, phenyl, 2,4-dinitrophenyl or phenylsulfonyl, very particularly preferably hydrogen, 2,4-dinitrophenyl or phenylsulfonyl and in particular hydrogen or 2,4-dinitrophenyl.
  • FG is preferably —Cl, —CN, —OCN, —SCN, —N + R 6 R 7 R 8 , —O(CO)R 5 , —O(CO)OR 5 , —(SO)Cl, —(SO 2 )R 5 , —(SO 2 )OR 5 or —O(CO)Cl.
  • FG is particularly preferably —Cl, —CN, —OCN, —SCN, —N + R 6 R 7 R 8 , —O(CO)R 5 , —O(CO)OR 5 or —(SO 2 )R 5 .
  • FG is very particularly preferably —Cl, —O(CO)R 5 , —O(CO)OR 5 or —(SO 2 )R 5 and in particular —Cl or —(SO 2 )R 5 .
  • R 5 is preferably methoxy, ethoxy, n-propoxy, n-butoxy, methyl, ethyl, n-propyl, n-butyl, tert-butyl, phenyl, 4-methylphenyl, trifluoromethyl or 4-bromophenyl.
  • R 5 is particularly preferably methoxy, ethoxy, n-butoxy, methyl, ethyl, n-butyl, phenyl, 4-methylphenyl, trifluoromethyl or 4-bromophenyl.
  • R 5 is very particularly preferably n-butoxy, methyl, ethyl, n-butyl, phenyl or 4-methylphenyl and in particular methyl or 4-methylphenyl.
  • R 6 , R 7 and R 8 independently of one another, are preferably methyl, ethyl, n-propyl, n-butyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl or 2-butoxycarbonylethyl.
  • R 6 , R 7 and R 8 independently of one another, are particularly preferably methyl, benzyl, 2-hydroxyethyl, 2-cyanoethyl, 2-methoxycarbonylethyl, 2-ethoxycarbonylethyl or 2-butoxycarbonylethyl.
  • R 6 , R 7 and R 8 independently of one another, are very particularly preferably methyl, benzyl, 2-hydroxyethyl or 2-butoxycarbonylethyl and in particular methyl, 2-hydroxyethyl or 2-butoxycarbonylethyl.
  • R 2 is 4-methylphenyl, 4-methoxyphenyl, 4-chlorophenyl, methoxy, n-propoxy, iso-propoxy, n-butoxy, sec-butoxy, iso-butoxy or tert-butoxy.
  • R 1 is ortho-substituted, for example 2-methylphenyl, 2-methoxyphenyl or 2-chlorophenyl.
  • acyl- and bisacylphosphine derivatives (I) according to the invention can be prepared by a process in which a substance of the formula (II)
  • R 1 , R 2 , Y and Z are as defined above, and
  • X is hydrogen or a cation
  • Cations here can be, for example, those as listed in EP-A 62 839, i.e. equivalents of a cation from main group 1 to 3 of the Periodic Table having a molecular weight of less than 138, or ammonium ions derived from quaternary ammonium ions or triethylenediammonium ions.
  • Agents which convert the —OX group into the —FG group are known per se to the person skilled in the art. Examples which may be mentioned are phosgene (COCl 2 ), thionyl chloride (SOCl 2 ), sulfuryl chloride (SO 2 Cl 2 ), phosphorus trichloride (PCl 3 ), phosphorus oxide trichloride (POCl 3 ), phosphorus pentachloride (PCl 5 ), oxalyl chloride ((COCl) 2 ), hydrogen chloride (HCl), chlorine gas (Cl 2 ), N-chloro compounds, for example N-chlorosuccinimide, alkali metal fluorides, cobalt(III) fluoride, halogen fluorides, antimony fluorides, molybdenum fluoride, hydrogen fluoride, hydrogen fluoride/pyridine mixtures, xenon fluorides and other noble-gas compounds, gaseous fluorine, sulfur tetrafluoride,
  • suitable agents can be, for example: bromine, alkali metal hypobromite, bromine iodide, cyanogen bromide, PBr 3 , PBr 5 , POBr 3 , SOBr 2 , N-bromosuccinimide, N-bromoacetamide and 1,3-dibromo-5,5-dimethylhydantoin.
  • the leaving group FG also contains a reactive center, as in the case of the reaction with phosgene, thionyl chloride, sulfuryl chloride, oxalyl chloride, etc., it is possible to react this reactive center again, for example with an alcohol R 5 OH, so that —(CO)Cl, —(SO)Cl, —(SO 2 )Cl groups, etc., are converted into —(CO)OR 5 , —(SO)OR 5 or —(SO 2 )OR 5 groups respectively.
  • the substrate to be reacted is usually initially introduced in the presence of from 0.9 to 1.5 mol equivalents of an acid scavenger, such as pyridine or a tertiary amine, for example triethylamine, tributylamine, benzyldimethylamine, dimethylaminopyridine, etc., at temperatures between 0° C. and 100° C., preferably between 10° C.
  • a suitable solvent for example benzene, toluene, xylene, tetrahydrofuran, hexane, heptane, pentane or petroleum ether
  • an acid scavenger such as pyridine or a tertiary amine, for example triethylamine, tributylamine, benzyldimethylamine, dimethylaminopyridine, etc.
  • the agent is added with vigorous mixing over a period of from a few minutes to several hours, preferably from 10 to 300 minutes, particularly preferably from 30 to 180 minutes. Stirring can be continued if desired, for example for from 30 to 600 minutes, preferably from 60 to 300 minutes, during which the reaction temperature can slowly be raised in steps.
  • the resultant reaction product can be processed further in crude or purified form.
  • the product can be purified, for example, by crystallization and solid/liquid separation or by distillation or rectification under reduced pressure.
  • the yields are generally greater than 75%, usually greater than 80% and frequently greater than 90%.
  • a metal halide (MeHal) for example LiCl, LiBr, LiI, NaCl, NaBr, NaI, KCl, KBr or KI
  • X corresponds to the metal (Me) used.
  • ionic liquids here is taken to mean ionic compounds which are liquid under the reaction conditions and/or work-up conditions.
  • the melting points of the preferred ionic liquids are generally below 160° C., particularly preferably below 100° C. and very particularly preferably below 80° C.
  • R is as defined above for C 1 -C 18 -alkyl which is unsubstituted or substituted by aryl, alkyl, aryloxy, alkoxy, heteroatoms and/or heterocyclic radicals, preferably methyl, ethyl or n-butyl.
  • R 1 , R 2 , Y and Z are as defined above.
  • halides here is taken to mean fluoride, chloride, bromide or iodide, preferably bromide or chloride and particularly preferably chloride.
  • Compounds of this type which can be employed as bases can contain phosphorus, sulfur or nitrogen atoms, for example at least one nitrogen atom, preferably from one to ten nitrogen atoms, particularly preferably from one to five nitrogen atoms, very particularly preferably from one to three nitrogen atoms and in particular one or two nitrogen atoms. If desired, further heteroatoms, for example oxygen, sulfur, phosphorus or halogen atoms, may also be present.
  • Particularly preferred compounds are those which have a molecular weight of less than 1000 g/mol, very particularly preferably less than 500 g/mol and in particular less than 250 g/mol.
  • pyridines particularly preference is given to pyridines, pyridazines, pyrimidines, pyrazines, imidazoles, 1H-pyrazoles, 3H-pyrazoles, 4H-pyrazoles, 1-pyrazolines, 2-pyrazolines, 3-pyrazolines, imidazolines, thiazoles, oxazoles, 1,2,4-triazoles or 1,2,3-triazoles, of which the pyridines and imidazoles are preferred.
  • the very particularly preferred bases are 3-chloropyridine, 4-dimethylaminopyridine, 2-ethyl-4-aminopyridine, 2-methylpyridine, 2-ethylpyridine, 2-ethyl-6-methylpyridine, quinoline, isoquinoline, pyridine, 1-C 1 -C 4 -alkylimidazole, 1-methylimidazole, 1,2-dimethylimidazole, 1-n-butylimidazole, 1,4,5-trimethylimidazole, 1,4-dimethylimidazole, imidazole, 2-methylimidazole, 1-butyl-2-methylimidazole, 4-methylimidazole, 1-n-pentylimidazole, 1-n-hexylimidazole, 1-n-octylimidazole, 1-(2′-aminoethyl)imidazole, 2-ethyl-4-methylimidazole, 1-vinylimidazole, 2-ethylimid
  • temperatures of 40-160° C. preferably 50-150° C., particularly preferably 60-140° C., very particularly preferably 80-130° C. and in particular 90-120° C.
  • the reaction is preferably carried out in the presence of a gas which is inert under the reaction conditions; this is particularly preferably passed through the reaction mixture.
  • a slight reduced pressure is applied, for example 200-900 mbar, preferably 300-800 mbar and particularly preferably 500-750 mbar, in order to simplify separation of the alkyl halide formed.
  • the reaction mixture can subsequently be diluted with water and the acid (III) liberated using a suitable strong acid, for example sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, formic acid or acetic acid, preferably with the strong acid which corresponds to the halide employed.
  • a suitable strong acid for example sulfuric acid, hydrochloric acid, hydrobromic acid, nitric acid, formic acid or acetic acid, preferably with the strong acid which corresponds to the halide employed.
  • the acid (III) where X ⁇ H can subsequently be separated off by solid-liquid or liquid-liquid separation and, if necessary, purified further.
  • acyl- and bisacylphosphine derivatives according to the invention can be used as photoinitiators for the radiation curing of photopolymerizable compositions, for example coating compositions, surface coatings, printing inks, recording materials, aqueous solutions, dispersions and emulsions.
  • the photoinitiators according to the invention can of course also be used in the form of a mixture with other photoinitiators.
  • These can be, for example, photoinitiators known to the person skilled in the art, for example those mentioned in “Advances in Polymer Science”, Volume 14, Springer Berlin, 1974, or in K. K. Dietliker, Chemistry and Technology of UV- and EB-Formulation for Coatings, Inks and Paints, Volume 3; Photoinitiators for Free Radical and Cationic Polymerization, P. K. T. Oldring (Eds), SITA Technology Ltd, London.
  • Suitable are, for example, mono- or bisacylphosphine oxides as described, for example, in EP-A 7 508, EP-A 57 474, DE-A 196 18 720, EP-A 495 751 or EP-A 615 980, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin® TPO from BASF AG), ethyl 2,4,6-trimethylbenzoylphenyl phosphinate (Lucirin® TPO L from BASF AG), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (Irgacure® 819 from Ciba Spezialitätenchemie), benzophenones, hydroxyacetophenones, phenylglyoxylic acid and derivatives thereof, or mixtures of these photoinitiators.
  • 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin® TPO from BASF AG), eth
  • Examples which may be mentioned are benzophenone, acetophenone, acetonaphthoquinone, methyl ethyl ketone, valerophenone, hexanophenone, ⁇ -phenylbutyrophenone, p-morpholinopropiophenone, dibenzosuberone, 4-morpholinobehzophenone, 4-morpholinodeoxybenzoin, p-diacetylbenzene, 4-aminobenzophenone, 4′-methoxyacetophenone, ⁇ -methylanthraquinone, tert-butylanthraquinone, anthraquinonecarboxylic acid esters, benzaldehyde, ⁇ -tetralone, 9-acetylphenanthrene, 2-acetylphenanthrene, 10-thioxanthenone, 3-acetylphenanthrene, 3-acetylindole, 9-fluorenone, 1-indan
  • photoinitiators of the phenylglyoxalic acid ester type which have little or no tendency toward yellowing, as described in DE-A 198 26 712, DE-A 199 13 353 or WO 98/33761.
  • acyl- and bisacylphosphine derivatives of the formula (I) according to the invention or the compounds prepared by the process according to the invention are particularly suitable as starting compounds for the preparation of novel photoinitiators, for example those described in the German patent applications with the title “Alkoxylated Mono- and Bisacylphosphine Derivatives” and the file reference 102 06 097.5 and the title “Mono- and Bisacylphosphine Derivatives” and the file reference 102 06 096.7 with the application date Feb. 13, 2002.
  • the compounds (I) according to the invention can be chemically coupled to compounds which contain, for example, free hydroxyl, amino, monoalkylamino, monoarylamino and/or mercapto groups.
  • These can preferably be compounds which are themselves polymerizable compounds, i.e. carry at least one (co)polymerizable group, or compounds which carry a group which acts as photoinitiator, for example acylphosphine oxides, bisacylphosphine oxides, benzophenones, acetophenones or phenylglyoxylic acid esters, or those which carry reactive groups which are themselves able to interact with a polymer.
  • (Co)polymerizable groups can be those which have unsaturated bonds, preferably carbon-carbon double bonds.
  • These can be, for example, free-radical- or cationically polymerizable groups.
  • Free-radical-(co)polymerizable groups are, for example, isolated ethylenically unsaturated groups, conjugated unsaturated groups, vinyl-aromatic groups, vinylic and vinylidene chloridic groups, N-vinylamides, vinylpyrrolidones, vinyl lactams, vinyl esters, (meth)acrylic esters or acrylonitriles.
  • Cationically (co)polymerizable groups are, for example, isobutylene units or vinyl ethers.
  • Compounds of this type which can be reacted with the acyl- and bisacylphosphine derivatives (I) according to the invention can be, for example, monoesters of a, ⁇ -unsaturated carboxylic acids, such as acrylic acid, methacrylic acid (abbreviated to “(meth)acrylic acid” in this specification), crotonic acid, itaconic acid, fumaric acid, maleic acid, acrylamidoglycolic acid, methacrylamidoglycolic acid, or vinyl ethers with diols or polyols, which preferably contain from 2 to 20 carbon atoms and at least two hydroxyl groups, such as ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,1-dimethyl-1,2-ethanediol, dipropylene glycol, tetraethylene glycol, pentaethylene glycol, tripropylene glycol, 1,4-butanedio
  • esters or amides of (meth)acrylic acid with aminoalcohols for example 2-aminoethanol, 2-(methylamino)ethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2-(2-aminoethoxy)ethanol, 2-mercaptoethanol or polyaminoalkanes, such as ethylenediamine or diethylenetriamine, or vinylacetic acid.
  • aminoalcohols for example 2-aminoethanol, 2-(methylamino)ethanol, 3-amino-1-propanol, 1-amino-2-propanol or 2-(2-aminoethoxy)ethanol, 2-mercaptoethanol or polyaminoalkanes, such as ethylenediamine or diethylenetriamine, or vinylacetic acid.
  • unsaturated polyetherols or polyesterols or polyacrylate-polyols which have a mean OH functionality of from 2 to 10 and preferably have a molecular weight of from 200 to 2000.
  • amides of ethylenically unsaturated carboxylic acids with aminoalcohols are hydroxyalkyl(meth)acrylamides, such as N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-hydroxyethylacrylamide, N-hydroxyethylmethacrylamide, 5-hydroxy-3-oxapentyl(meth)acrylamide,
  • N-hydroxyalkylcrotonamides such as N-hydroxymethylcrotonamide
  • N-hydroxyalkylmaleimides such as N-hydroxyethylmaleimide
  • acyl- and bisacylphosphine derivatives of the formula (I) according to the invention exhibit a migration tendency which is generally lower than most conventional acylphosphine oxide compounds, even without reaction with compounds containing polymerizable groups, since they are capable of reacting, through their reactive group FG, with reactive centers in the components which form the radiation-curable compositions, enabling the compounds according to the invention to be bonded, for example, to the binder of the radiation-curable compositions with formation of a chemical bond.
  • free hydroxyl, amino, monoalkylamino, monoarylamino and/or mercapto groups are capable of functioning as reactive centers in radiation-curable compositions.
  • the invention also relates to radiation-curable compositions which are obtainable by reaction of at least one acyl- or bisacylphosphine derivative of the formula (I) or prepared by the process according to the invention with a radiation-curable composition containing free hydroxyl, amino, monoalkylamino, monoarylamino and/or mercapto groups.
  • Suitable radiation-curable compositions comprise, for example, at least one polymerizable compound having one or more (co)polymerizable, ethylenically unsaturated groups and one or more reactive centers.
  • These can be, for example, urethane, melamine, polyesterol, polyetherol, epoxide or carbonate acrylates, methacrylates or vinyl ethers containing reactive centers.
  • urethane, melamine, polyesterol, polyetherol, epoxide or carbonate acrylates, methacrylates or vinyl ethers of this type is known per se to the person skilled in the art.
  • the number of reactive centers and ethylenically unsaturated groups can be adjusted through suitable mixing of the individual components.
  • the number average molecular weight M n of the polymerizable compounds which can be employed is not restricted. It can be, for example, below 20,000, preferably below 15,000, particularly preferably below 10,000 and in particular below 6000.
  • the polydispersity M w /M n represents a measure of the molecular weight distribution of the polymerizable compounds and in the ideal case has the value 1, but in practice values below 4.0, in particular below 3.5, are also satisfactory.
  • the data on the polydispersity and the number average and weight average molecular weights M n and M w are based here on gel permeation chromatography measurements, with polystyrene as standard and tetrahydrofuran as eluent. The method is described in Analytiker Taschenbuch, Vol. 4, pages 433 to 442, Berlin, 1984.
  • the compounds of the formula (I) according to the invention react, after mixing with the radiation-curable composition, with the reactive centers thereof and are thus bound in a migration-resistant manner.
  • the coating compositions prepared with the incorporable photoinitiators according to the invention are particularly suitable for use in packaging systems, particularly preferably in the foods sector.
  • compositions which have from 0.005 to 0.5 mol, particularly preferably 0.01-0.3 mol, very particularly preferably 0.05-0.2 mol and in particular 0.07-0.15 mol of hydroxyl groups per 100 g of substance.
  • acyl- and bisacylphosphine derivatives of the formula (I) according to the invention are usually used per mol of hydroxyl groups in the radiation-curable composition.
  • the bonding of the compounds of the formula (I) according to the invention to the reactive centers is generally carried out at a temperature between room temperature and the curing temperature of the radiation-curable composition obtainable in this way. Typical temperatures are 40-120° C., preferably 50-110° C. and particularly preferably 60-100° C.
  • the temperature can be kept constant or increased.
  • the duration of the thermal treatment is generally between a few minutes and several hours, for example from 1 minute to 5 hours, preferably from 2 minutes to 3 hours, particularly preferably from 5 minutes to 2 hours and in particular from 10 minutes to 1 hour.
  • R 9 is hydrogen or C 1 - to C 4 -alkyl
  • R 3 and R 4 are as defined above.
  • Radiation-curable compositions typically comprise
  • compositions are, for example,
  • the proportion of additives (D) which are typical in surface coatings can be up to 90% by weight. In this case, the proportions of the other components are reduced correspondingly.
  • Compounds (A) can be, for example, the urethane, melamine, polyesterol, polyetherol, epoxide or carbonate acrylates, methacrylates or vinyl ethers mentioned above.
  • the compounds (A) are preferably vinyl ether or (meth)acrylate compounds, particularly preferably in each case the acrylate compounds, i.e. the derivatives of acrylic acid.
  • Preferred vinyl ether and (meth)acrylate compounds (A) contain from 2 to 20, preferably from 2 to 10 and very particularly preferably from 2 to 6 copolymerizable, ethylenically unsaturated double bonds.
  • compounds (A) having a content of ethylenically unsaturated double bonds of 0.1-0.7 mol/100 g, very particularly preferably 0.2-0.6 mol/100 g.
  • Suitable reactive thinners are free-radical-polymerizable compounds, preferably radiation-curable compounds containing an ethylenically unsaturated, copolymerizable group, or mixtures thereof.
  • (meth)acrylic acid is used for acrylic acid and methacrylic acid.
  • ⁇ , ⁇ -Unsaturated carboxylic acids which can be used are, for example, acrylic acid, methacrylic acid, maleic acid or monoesters thereof, 3-acryloxypropionic acid, maleic anhydride, fumaric acid or monoesters thereof, or crotonic acid.
  • Preferred alkyl(meth)acrylates are those containing a C 1 -C 10 -alkyl radical, such as methyl methacrylate, methyl acrylate and ethyl acrylate.
  • Vinyl esters of carboxylic acids having from 1 to 20 carbon atoms are, for example, vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate.
  • Suitable vinylaromatic compounds are, for example, vinyltoluene, ⁇ -butylstyrene, 4-n-butylstyrene, 4-n-decylstyrene and preferably styrene.
  • nitriles are acrylonitrile and methacrylonitrile.
  • vinyl ethers examples include vinyl methyl ether, vinyl isobutyl ether, vinyl hexyl ether and vinyl octyl ether.
  • Non-aromatic hydrocarbons having from 2 to 8 carbon atoms and one or two olefinic double bonds which may be mentioned are butadiene, isoprene, as well as ethylene, propylene and isobutylene.
  • N-vinylformamide N-vinylpyrrolidone and N-vinylcaprolactam.
  • the additives (D) which are typical in surface coatings can be, for example, antioxidants, oxidation inhibitors, stabilizers, activators (accelerators), fillers, pigments, dyes, degassing agents, luster agents, antistatic agents, flame inhibitors, thickeners, thixotropic agents, flow-control agents, binders, antifoaming agents, fragrances, surface-active agents, viscosity modifiers, plasticizers, tackifying resins (tackifiers), chelating agents or compatibilizers.
  • antioxidants for example, antioxidants, oxidation inhibitors, stabilizers, activators (accelerators), fillers, pigments, dyes, degassing agents, luster agents, antistatic agents, flame inhibitors, thickeners, thixotropic agents, flow-control agents, binders, antifoaming agents, fragrances, surface-active agents, viscosity modifiers, plasticizers, tackifying resins (tackifiers), chelating agents or compatibilizer
  • the coating of substrates with the radiation-curable compositions is carried out by conventional methods known to the person skilled in the art, in which at least one radiation-curable composition according to the invention, for example in the form of a dispersion or alternatively without a solvent, is applied in the desired thickness to the substrate to be coated, and the volatile constituents of the dispersion are removed, if necessary with heating. This operation can, if desired, be repeated one or more times.
  • the application to the substrate can be carried out in a known manner, for example by spraying, dipping, knife coating, using an air blade, brushing, rolling or curtain coating.
  • the coating thickness is generally in the range from about 3 to 1000 g/m 2 and preferably from 10 to 200 g/m 2 .
  • a coating composition comprising a substance according to the invention, if desired as a surface-coating formulation to which further additives which are typical in surface coatings and/or thermally curable resins have been added, is applied to the substrate, if desired dried, thermally treated at the curing temperature indicated above, and subsequently cured, if desired at temperatures up to the level of the curing temperature, with active radiation under an oxygen-containing atmosphere, for example air, or preferably under an inert gas.
  • an oxygen-containing atmosphere for example air, or preferably under an inert gas.
  • the process for the coating of substrates can also be carried out by, after application of the mixture or surface-coating formulation according to the invention, firstly effecting curing with active radiation under an oxygen-containing atmosphere, for example air, or preferably under an inert gas, and subsequently carrying out a thermal treatment at the curing temperature.
  • an oxygen-containing atmosphere for example air, or preferably under an inert gas
  • the curing of the films formed on the substrate can, if desired, be carried out exclusively thermally. In general, however, the coatings are cured both by irradiation with high-energy radiation and also thermally.
  • thermal and/or radiation curing can be carried out after each coating operation.
  • active energy rays are ultraviolet rays, X-rays and electron beams, preferably ultraviolet rays and electron beams.
  • the coating of substrates can also be carried out as follows:
  • Steps iv) and iii) can also be carried out in the reverse sequence, i.e. the film can firstly be cured thermally and then with high-energy radiation.
  • Typical curing temperatures are 40-120° C., preferably 50-110° C. and particularly preferably 60-100° C.
  • the temperature can be kept constant or increased.
  • the curing duration is generally between a few minutes and several hours, for example from 1 minute to 5 hours, preferably from 2 minutes to 3 hours, particularly preferably from 5 minutes to 2 hours and in particular from 10 minutes to 1 hour.
  • Suitable radiation sources for the radiation curing are, for example, mercury low-pressure emitters, medium-pressure emitters or high-pressure emitters and fluorescent tubes, pulsed emitters, metal-halide emitters, xenon lamps, electrode-less discharge lamps, carbon arc lamps, electronic flash devices, which enable radiation curing without a photoinitiator, or excimer emitters.
  • the radiation curing is carried out through exposure to high-energy radiation, i.e.
  • the radiation sources used are, for example, high-pressure mercury vapor lamps, lasers, pulsed lamps (flashlight), halogen lamps or excimer emitters.
  • the radiation dose which is usually sufficient for crosslinking in the case of UV curing is in the range from 80 to 3000 mJ/cm 2 .
  • the photoinitiators according to the invention can also be employed with a radiation source having a low or even no UV content.
  • Daylight curing is likewise possible, albeit generally slower than curing with active energy radiation.
  • the absorption spectrum of the compound I-1 essentially corresponds to that of Lucirin TPO, it being crucial that the absorption range extends into the region of visible light.
  • the irradiation can, if desired, also be carried out with exclusion of oxygen, for example under an inert-gas atmosphere. Suitable inert gases are preferably nitrogen, noble gases, carbon dioxide, or combustion gases.
  • the irradiation can furthermore be carried out by masking the coating composition with transparent media. Transparent media are, for example, plastic films, glass or liquids, for example water. Irradiation is particularly preferably carried out in the manner as described in DE-A 199 57 900.
  • Parts here are taken to mean “parts by weight”, unless specified otherwise.
  • ethyl trimethylbenzoylphenylphosphinate (Lucirin® TPO-L, BASF AG) were initially introduced in 3000 ml of ethyl methyl ketone, and 1.1 equivalents (285 g) of sodium iodide were added to the solution. After 15 minutes, the homogeneous solution was heated to 65° C. and stirred for 24 hours. The yellow precipitate was filtered off with suction and washed with 2 ⁇ 500 ml of petroleum ether. The filter cake was dried at 60° C. under reduced pressure. 530 g (85% of theory) of pale-yellow powder were isolated.
  • the crude product was recrystallized from 40 ml of ethyl acetate and dried. 7.42 g of trimethylbenzoylphenylphosphinic acid were isolated. The content according to HPLC was >98%.

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US9644068B2 (en) 2012-12-18 2017-05-09 Basf Se Semiconducting materials based on naphthalenediimide-vinylene-oligothiophene-vinylene polymers
EP3459957A1 (de) 2012-12-19 2019-03-27 IGM Group B.V. Derivate von bisacylphosphinsäure, deren herstellung und verwendung als photoinitiatoren

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